CN111762968A - Comprehensive treatment method and system for refractory high-concentration wastewater - Google Patents

Comprehensive treatment method and system for refractory high-concentration wastewater Download PDF

Info

Publication number
CN111762968A
CN111762968A CN202010613151.XA CN202010613151A CN111762968A CN 111762968 A CN111762968 A CN 111762968A CN 202010613151 A CN202010613151 A CN 202010613151A CN 111762968 A CN111762968 A CN 111762968A
Authority
CN
China
Prior art keywords
wastewater
integrated
catalytic oxidation
filler
ozone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010613151.XA
Other languages
Chinese (zh)
Inventor
李萌
陈倩
韩少科
贠小淇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Xinlin Water Technology Co ltd
Original Assignee
Beijing Xinlin Water Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Xinlin Water Technology Co ltd filed Critical Beijing Xinlin Water Technology Co ltd
Priority to CN202010613151.XA priority Critical patent/CN111762968A/en
Publication of CN111762968A publication Critical patent/CN111762968A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/14—NH3-N
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

The invention relates to the field of wastewater treatment systems, in particular to a method and a system for comprehensively treating refractory high-concentration wastewater. According to the flow direction of wastewater treatment, the system comprises a pretreatment section, a front multi-phase catalytic oxidation integrated device, a high-concentration wastewater integrated biochemical treatment device and a rear multi-phase catalytic oxidation integrated device. According to the front multi-phase catalytic oxidation integrated equipment of the wastewater treatment system, the synergistic effect of ozone, hydrogen peroxide and iron-carbon filler is utilized, hydroxyl radicals are continuously generated, organic matters which are difficult to biodegrade are degraded, and the oxidation efficiency is obviously improved.

Description

Comprehensive treatment method and system for refractory high-concentration wastewater
Technical Field
The invention relates to the field of wastewater treatment systems, in particular to a method and a system for comprehensively treating refractory high-concentration wastewater.
Background
The quality of industrial wastewater is characterized in that the components of wastewater pollution are complex, the concentrations of COD, oils and salts are high, and the biodegradability is poor, and multiple process combinations such as physical separation, chemical treatment, biological treatment and the like are generally adopted to treat multi-component pollutants so as to convert the multi-component pollutants into harmless substances for discharge.
The problems of most of the currently used wastewater treatment systems are that: 1) the advanced oxidation unit is arranged at the front end of the biochemical unit, and macromolecular organic matters which are difficult to biodegrade are decomposed into micromolecular organic matters which are easy to degrade, so that the biodegradability of the wastewater is improved, but the efficiency of generating hydroxyl radicals at the advanced oxidation section is low, and the treatment effect of the subsequent biochemical unit is directly influenced; 2) the monomer treatment unit usually needs additional feeding to assist in removing pollutants, but internal products can cause secondary pollution, and the difficulty and cost of subsequent treatment are increased; 3) the treatment system has limited removal capacity for COD, ammonia nitrogen, total nitrogen and total phosphorus and can not reach the effluent standard.
Disclosure of Invention
The invention aims to provide a novel intelligent comprehensive treatment system for high-concentration wastewater difficult to degrade, so as to solve the problems in the background technology.
The invention further aims to provide a novel intelligent comprehensive treatment method for the high-concentration wastewater difficult to degrade.
According to the comprehensive treatment system for the refractory high-concentration wastewater, according to the wastewater treatment flow direction, the comprehensive treatment system comprises a pretreatment section, a front multi-phase catalytic oxidation integrated device, a high-concentration wastewater integrated biochemical treatment device and a rear multi-phase catalytic oxidation integrated device, wherein a gas distribution system and a catalytic filler are installed in a catalytic oxidation reaction tower of the front multi-phase catalytic oxidation integrated device, ozone gas enters from the bottom of a reaction tower through the gas distribution system, the ozone gas is required to be introduced as an oxidant when the ozone gas is introduced, the catalytic filler filled in a hydrogen peroxide solution tower is an iron-carbon filler, the addition amount of the ozone is 0.1-10 mg/mg of COD wastewater, the addition amount of the hydrogen peroxide solution is 1-50 mg/mg of COD, and the addition mass ratio of the ozone, the hydrogen peroxide solution and the iron-carbon filler is 1:2: 2-4: 2.
According to the integrated treatment system for the high-concentration wastewater difficult to degrade, disclosed by the invention, a submersible stirrer is arranged in a regulating hydrolysis contact tank of the integrated biochemical treatment device for the high-concentration wastewater.
According to the degradation-resistant high-concentration wastewater comprehensive treatment system, the baffle plates are vertically arranged in the multiphase anaerobic baffling contact reaction tank of the high-concentration wastewater integrated biochemical treatment device, and the tank body is divided into a multi-compartment structure.
According to the integrated treatment system for the high-concentration wastewater difficult to degrade, disclosed by the invention, an aerobic filler and an aeration system are arranged in the biological contact oxidation tank of the integrated biochemical treatment device for the high-concentration wastewater.
The novel intelligent comprehensive treatment method for the refractory high-concentration wastewater comprises the following steps:
pre-treating;
the pretreated wastewater enters a pre-multiphase catalytic oxidation integrated device, macromolecule organic matters which are difficult to biodegrade are decomposed into micromolecule organic matters which are easy to be biodegraded by the synergistic action of ozone, hydrogen peroxide and iron carbon filler, the fallen carbon powder is discharged to a subsequent biochemical unit along with the oxidized wastewater, wherein, a gas distribution system and a catalytic filler are arranged in the catalytic oxidation reaction tower of the former multi-phase catalytic oxidation integrated equipment, ozone gas enters from the bottom of the reaction tower through the gas distribution system, when the ozone gas is introduced, hydrogen peroxide is introduced as an oxidant, the catalytic filler filled in the tower is iron-carbon filler, wherein the adding amount of ozone is 0.1-10 mg/mg COD wastewater, the adding amount of hydrogen peroxide is 1-50 mg/mg COD, and the adding mass ratio of ozone, hydrogen peroxide and iron carbon filler is 1:2: 2-4: 2: 3;
wastewater flowing to the high-concentration wastewater integrated biochemical treatment device sequentially passes through the adjusting hydrolysis tank, the multiphase anaerobic baffling contact reaction tank, the biological contact oxidation tank and the micro-aeration MBR tank, and forms a sludge membrane symbiotic microbial environment and a sludge system with multiple sludge ages in the biochemical system under the action of carbon powder and fillers to remove COD (chemical oxygen demand) and TN (total nitrogen) pollutants;
the biochemical effluent is discharged to a post-multiphase catalytic oxidation integrated device, in the device, macromolecular organic matters which are subjected to biochemical treatment and can not be degraded by renewable organisms are further oxidized into micromolecular organic matters, then the micromolecular organic matters flow back to a regulating hydrolysis tank to be removed under the action of microorganisms, and carbon powder falling off in the device flows back to a biochemical unit to become a biological carrier for use.
Compared with the prior art, the invention has the following beneficial effects:
1. the coupling of the former multi-phase catalytic oxidation integrated equipment, the high-concentration wastewater integrated biochemical treatment device and the latter multi-phase catalytic oxidation integrated equipment cooperatively treats the high-concentration industrial wastewater which is difficult to degrade, and realizes the high-efficiency removal of multi-component pollutants.
2. The former multi-phase catalytic oxidation integrated equipment continuously generates hydroxyl radicals by utilizing the synergistic effect of ozone, hydrogen peroxide and iron-carbon filler, degrades organic matters which are difficult to biodegrade, and obviously improves the oxidation efficiency.
3. The carbon powder dropped from the former multi-phase catalytic oxidation integrated equipment becomes a biological carrier of a subsequent biochemical unit, thereby realizing the recycling of the carbon powder, not only enhancing the biochemical treatment effect, but also reducing the treatment to solid wastes.
4. The integrated biochemical treatment device for the high-concentration wastewater comprises three biochemical methods of anoxic, anaerobic and aerobic and a membrane treatment method, and different special biological fillers are filled, so that a sludge-membrane symbiotic microbial environment and a sludge system with multiple sludge ages are formed in a biochemical system, and partial anaerobic ammonia oxidation denitrification is realized.
5. The integrated biochemical treatment device for high-concentration wastewater combines a novel micropore aeration technology and a membrane bioreactor technology, and improves the oxygen utilization rate and the water flux.
6. The high-concentration wastewater integrated biochemical treatment device is integrated into the fluid dynamics principle of a chemical reactor, optimizes the hydraulic flow state, improves the biochemical treatment capacity of the device, remarkably improves the removal rate of COD (chemical oxygen demand), total nitrogen and total phosphorus, and has low sludge production rate and stable effluent quality.
7. The effluent of the post-multiphase catalytic oxidation equipment flows back to the adjusting hydrolysis contact tank, so that the impact load resistance of the biochemical unit can be improved, and the concentration of the influent pollutants can be diluted; meanwhile, the fallen carbon powder is also brought into a biochemical unit to be used as a biological carrier.
8. The degradation-resistant high-concentration wastewater comprehensive treatment system has the advantages of high removal rate, high treatment efficiency, stable effluent quality, low sludge yield, small floor area, high system integration level and the like.
Drawings
FIG. 1 is a schematic structural diagram of a novel intelligent comprehensive treatment system for refractory high-concentration wastewater.
FIG. 2 shows the mass ratio of the added ozone, hydrogen peroxide and iron-carbon filler to COD and NH of wastewater4-removal effect of N.
FIG. 3 shows the mass ratio of the added ozone, hydrogen peroxide and iron-carbon filler to the added COD and NH of wastewater4-removal effect of N.
Reference numerals: 1-pretreatment section, 2-front multi-phase catalytic oxidation integrated equipment, 3-high concentration wastewater integrated biochemical treatment device and 4-rear multi-phase catalytic oxidation integrated equipment
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
As shown in figure 1, the comprehensive treatment system for high-concentration wastewater difficult to degrade comprises a pretreatment section 1, a front heterogeneous catalytic oxidation integrated device 2, a high-concentration wastewater integrated biochemical treatment device 3 and a rear heterogeneous catalytic oxidation integrated device 4 according to the wastewater treatment flow direction.
The former heterogeneous catalytic oxidation integration equipment sets up before high concentration waste water integration biochemical treatment device, install gas distribution system and catalytic filler in the catalytic oxidation reaction tower of preceding heterogeneous catalytic oxidation integration equipment, ozone gas gets into from the reaction tower bottom through the gas distribution system, and after fully mixing with the reactor water, passes through the filler district jointly, in the reaction tower, each component interact forms the hydroxyl free radical, improves the oxidation effect. Furthermore, when ozone gas is introduced into the catalytic oxidation reaction tower, hydrogen peroxide is required to be introduced as an oxidant, and the catalytic filler filled in the tower is an iron-carbon filler.
Technology for obtaining multiphase catalytic oxidation integrated equipment before settingThe effect is as follows: (1) at the initial stage of operation of the catalytic oxidation reaction tower, the tower is in a neutral or alkaline environment, ozone and hydrogen peroxide play a role in generating hydroxyl radicals, and the iron-carbon filler plays a role in catalysis and adsorption; (2) after excessive hydrogen peroxide is introduced, the tower is in an acid environment, and the iron-carbon filler and the electrolyte solution form a primary battery to perform electrolysis to generate hydroxyl radicals; (3) fe in solution as the electrolysis proceeds2+The hydrogen peroxide and the hydrogen peroxide solution form a reagent with extremely strong oxidizing capability again to generate more hydroxyl radicals; (4) hydroxyl free radicals are continuously generated in the catalytic oxidation tower, macromolecular organic matters which are difficult to biodegrade are oxidized, and the treatment efficiency is improved; (5) the carbon powder falling off from the catalytic oxidation tower flows into a subsequent biochemical unit along with water flow to become a biological carrier, so that the concentration of activated sludge is improved, the sludge age is prolonged, a certain adsorption function is realized, and the removal rate of organic matters, ammonia nitrogen, total nitrogen and total phosphorus is greatly improved.
The amount of ozone introduced into the catalytic oxidation reaction tower is 0.1-10 mg/mg of COD wastewater, the adding amount of hydrogen peroxide is 1-50 mg/mg of COD, and the adding mass ratio of the ozone to the hydrogen peroxide to the iron-carbon filler is 1:2: 2-4: 2: 3.
At the initial stage of the reaction, the initial pH is controlled to be more than or equal to 7, and OH is carried out under the condition-The iron-carbon filler has strong adsorption effect on organic matters and strong promotion effect on catalytic oxidation of ozone. In the reaction system, O3The optimal adding mass ratio of the iron-carbon filler to hydrogen peroxide is 1: 1-2: 1, the iron-carbon filler is used as a catalyst, the consumption problem does not exist, and in the process, the excessively low adding mass ratio can reduce O3The pH value of the solution is always acidic due to the excessively high adding mass ratio, and the subsequent reaction is influenced.
With O3After the decomposition is finished, continuously introduced hydrogen peroxide and organic matters which are difficult to degrade are oxidized and decomposed into micromolecular organic acids, so that the interior of the system is in an acid environment, the iron-carbon filler and the electrolyte solution form a primary battery, and hydroxyl radicals generated by electrolysis are continuously oxidized and decomposed into organic pollutants. This is achieved byIn addition, Fe generated at the anode of the battery is generated along with the uninterrupted progress of the reaction2+And the catalyst and hydrogen peroxide solution form a reagent with extremely strong oxidizing capability again, so that hydroxyl radicals are continuously generated in the whole reaction system, and the catalytic oxidation performance is obviously improved. And in the later reaction period, the optimal adding mass ratio of the hydrogen peroxide to the iron-carbon filler is 1: 2-1: 3. In this process, too low a mass ratio of addition reduces Fe2+An excessively high addition mass ratio results in an excess of Fe2+The catalyst has a masking effect on hydroxyl free radicals and reduces the efficiency of catalytic oxidation reaction.
In the former multi-phase catalytic oxidation system, the biodegradability index of the wastewater is in positive correlation with the adding amount of ozone, hydrogen peroxide and iron carbon filler, the effect tends to be stable after the adding mass ratio is 1:2: 2-4: 2:3, and the adding mass ratio is 1:2: 2-4: 2:3 and is a critical ratio.
Furthermore, a submersible stirrer is arranged in an adjusting hydrolysis contact pool of the high-concentration wastewater integrated biochemical treatment device to accelerate the process that insoluble organic matters are hydrolyzed into soluble organic matters by hydrolytic bacteria and acidifying bacteria, and the retention time in the adjusting hydrolysis contact pool is 4-24 h.
Baffle plates are vertically arranged in a multiphase anaerobic baffling contact reaction tank of the high-concentration wastewater integrated energy biochemical treatment device, and a tank body is divided into a multi-compartment structure, so that a staged multiphase anaerobic process is formed. The wastewater is baffled up and down in the tank body along the baffle plates to move forward, the baffle plates divide the internal structure of the tank body into an upward flow chamber and a downward flow chamber, and the structure is designed into a structure form that the upward flow chamber is widened and the downward flow chamber is narrowed. The lower part of the baffle plate is provided with a 45-degree guide plate. Anaerobic special biological fillers are selected in the compartments, a special and stable growth environment is provided for anaerobic microorganisms, and the microorganisms are rapidly propagated in the fillers. The anaerobic special biological filler is a suspended filler, and the specific surface area of the suspended filler is 380-800 m3Per square meter, the filling rate of the filler is 6-15 percent (by the stacking volume), the filling rate of the filler is 60-80 percent (by the filling volume), and the volume load is 0.8-3 kgBOD/m3A filler d.
For example, the multiphase anaerobic baffling contact reaction tank of the high-concentration wastewater integrated biochemical treatment device is designed into 4 compartments, but not limited to 4 compartments, and the multiphase anaerobic baffling contact reaction tank is specifically designed according to the specific situation of the COD index of the inlet water.
An aerobic filler and an aeration system are arranged in a biological contact oxidation tank of the high-concentration wastewater integrated biochemical treatment device, the aerobic special biological filler is a suspended filler, and the specific surface area of the filler is 250-260 m3Per square meter, the filling rate of the filler is 4-15% (by stacking volume), the filling rate of the filler is 40-80% (by filling volume), and the volume load is 0.4-2.0 kgBOD/m3Filler d, 0.5-1.0 kg TKN/m3D, filling, wherein the aeration system comprises a disc type aeration head, aeration branch pipes, an aeration main pipe and an aeration fan, and dissolved oxygen is controlled to be 2-4mg/L in the tank.
The biological contact oxidation tank of the high-concentration wastewater integrated biochemical treatment device is designed into a multistage series working mode, and can realize the random switching in an anoxic working mode or an aerobic working mode by controlling the oxygen supply amount of the aeration fan.
When the biological contact oxidation tank of the high-concentration wastewater integrated biochemical treatment device is in an anoxic tank, an anoxic filler and an aeration system are installed in the tank, the anoxic special biological filler is a suspended filler, and the specific surface area of the filler is 300-500 m3Per square meter, the filling rate of the filler is 5-15% (by stacking volume), the filling rate of the filler is 50-80% (by filling volume), and the volume load is 0.5-2.0 kgBOD/m3D, filling, wherein the aeration system comprises a disc type aeration head, aeration branch pipes, an aeration main pipe and an aeration fan; the dissolved oxygen in the pool is controlled to be 0.3-0.8 mg/L.
A membrane module and an aeration system are arranged in a micro-aeration MBR tank of the high-concentration wastewater integrated biochemical treatment device. When the mud yield of the front-end system is large, the membrane component is a membrane with a lining, the strength is high, the pore diameter distribution is wide, the pores are large, and the membrane can resist cleaning; when the mud yield of the front-end system is small, the membrane component is a membrane with small strength, narrow pore size distribution and small pores; the aeration system comprises a microporous aerator, aeration branch pipes, an aeration main pipe and an aeration fan.
The back heterogeneous catalytic oxidation integration equipment sets up in high concentration waste water integration biochemical treatment device's rear end to go out water reflux to adjust in the contact tank of hydrolysising, the technological effect that heterogeneous catalytic oxidation integration was established after setting up is: (1) macromolecular organic matters which cannot be degraded by renewable substances can be further oxidized into micromolecular organic matters which are then removed under the action of microorganisms; (2) the concentration of the pollutants entering the biochemical reaction system is diluted by the backflow of the wastewater, so that the impact of the high-concentration pollutants on microorganisms is reduced, and the removal effect is improved; (3) the carbon powder dropped off by the later multi-phase catalytic oxidation integrated equipment can enter a biochemical system to become an effective microorganism carrier.
The principle of the degradation-resistant high-concentration wastewater comprehensive treatment system for purifying wastewater is as follows: the wastewater firstly passes through a pretreatment section, and flows to the former multi-phase catalysis integrated equipment after removing large suspended substances, grease, salt and other pollutants by a physical method; in the heterogeneous catalytic oxidation integrated equipment, through the synergistic effect of ozone, hydrogen peroxide and iron-carbon filler, macromolecular organic matters which are difficult to biodegrade are decomposed into micromolecular organic matters which are easy to be biodegraded, the biodegradability of waste water is improved, and the fallen carbon powder is discharged to a subsequent biochemical unit along with the oxidized waste water; wastewater flowing to the high-concentration wastewater integrated biochemical treatment device sequentially passes through the adjusting hydrolysis tank, the multiphase anaerobic baffling contact reaction tank, the biological contact oxidation tank and the micro-aeration MBR tank, and forms a sludge membrane symbiotic microbial environment and a sludge system with multiple sludge ages in the biochemical system under the action of carbon powder and fillers, so that pollutants such as COD (chemical oxygen demand), TN (total nitrogen) and the like are efficiently removed; the biochemical effluent is discharged to a post-multiphase catalytic oxidation integrated device, in the device, macromolecular organic matters which are subjected to biochemical treatment and can not be degraded by renewable organisms are further oxidized into micromolecular organic matters, then the micromolecular organic matters flow back to a regulating hydrolysis tank to be removed under the action of microorganisms, and carbon powder falling off in the device also flows back to a biochemical unit to become a biological carrier for use.
The invention is further explained below by means of actual engineering case data.
Example 1
In this example, the amount of wastewater discharged by a pharmaceutical intermediate manufacturing enterprise in Hebei is 200m3And d. The wastewater is mainly wastewater generated in the production process of drug intermediates and workshop spray wastewaterAnd domestic wastewater, the CODcr value of the wastewater is high (COD is less than or equal to 15000mg/L), and the ammonia nitrogen content is high (NH)4-N≤1000mg/L)。
And (4) water outlet standard: COD < 150mg/L, NH4-N＜20mg/L。
The wastewater is treated by adopting a regulating tank, coagulating sedimentation, ammonia nitrogen stripping, pre-multiphase catalytic oxidation, high-concentration wastewater integrated intelligent biochemical treatment and post-multiphase catalytic oxidation, wherein the mass ratio of ozone, hydrogen peroxide and iron-carbon filler is as follows: 1:2:2. The quality and removal rate of the feed water to each stage are shown in Table 1 below.
TABLE 1
Figure BDA0002561238510000071
Example 2
The results of comparison of the oxidation effects of ozone oxidation, ozone + hydrogen peroxide, and ozone + hydrogen peroxide + iron carbon filler are shown in table 2 below.
TABLE 2 advanced Oxidation Effect comparison Table
Figure BDA0002561238510000072
As can be seen from Table 2, the same raw water (COD:1000mg/L, B/C:0.15) was tested in O3、O3+H2O2、 O3+H2O2+ high oxidation effect of iron-carbon filler in different systems. Wherein, the control of the adding amount of ozone (2mg/mgCOD), the adding amount of hydrogen peroxide (5mg/mgCOD) and the reaction time (60min) are the same, and the result shows that the advanced oxidation effect is as follows: o is3+H2O2+ iron-carbon filler (B/C:0.61)>O3+H2O2(B/C:0.45)>O3(B/C:0.31)。
The results of comparison of the treatment effects of the biochemical units are shown in Table 3, in which the biochemical influent water corresponds to the 3 types of advanced oxidation effluent water in Table 2.
TABLE 3 comparison table of biochemical effect
Figure BDA0002561238510000073
Figure BDA0002561238510000081
As can be seen from Table 3, the same raw water (COD:1000mg/L, B/C:0.15) was tested in O3、O3+H2O2、 O3+H2O2The effect of the advanced oxidation under different systems of the iron-carbon filler and the effect of the corresponding advanced oxidation unit on the subsequent biochemical unit. Wherein the ozone dosage (2mg/mgCOD), the hydrogen peroxide dosage (5mg/mgCOD), the reaction time (60min) and the biochemical unit setting (high-concentration wastewater integrated biochemical treatment device) are controlled to be the same; the results show that: advanced oxidation effect: o is3+H2O2+ iron-carbon filler (B/C:0.61)>O3+H2O2(B/C:0.45)>O3(B/C:0.31), Biochemical treatment Effect: o is3+H2O2+ iron-carbon filler + high concentration wastewater integrated biochemical treatment device (wherein, the fallen carbon powder is used as biological carrier, strengthening carrier system, COD removal rate is 80%, NH4-The N removal rate: 75%)>O3+H2O2+ high concentration wastewater integrated biochemical treatment device (COD removal rate: 75%, NH)4-The N removal rate: 60%)>O3+ high concentration wastewater integrated biochemical treatment device (COD removal rate: 70%, NH)4-The N removal rate: 53%).
Further, the former heterogeneous catalytic oxidation + high concentration wastewater integrated biochemical treatment device + the latter heterogeneous catalytic oxidation treatment effect are shown in table 4 below.
Table 4 pollutant removing effect table of novel intelligent comprehensive treatment system for high-concentration wastewater difficult to degrade
Figure BDA0002561238510000082
As can be seen from Table 4, the raw water (COD:1000mg/L, B/C:0.15) was successively subjected to the former heterogeneous catalytic oxidation (O)3+H2O2+ iron-carbon filler) and high-concentration wastewater integrationBiochemical treatment device (filler and fallen carbon powder are used as biological carrier together), and post-multiphase catalytic oxidation (O)3+H2O2+ iron carbon filler) the results show: the removal rate of COD of the system reaches 85 percent, and the removal rate of NH of the system4-The removal rate of N reaches 80 percent.
Example 3
In this example, the wastewater was the same drug intermediate wastewater as in example 1, and the mass ratio of ozone, hydrogen peroxide, and iron-carbon filler was changed in a laboratory bench, and the obtained experimental data are shown in table 5 below.
TABLE 5
Figure BDA0002561238510000091
As shown in table 5 and fig. 2, inside the catalytic oxidation system, as the mass ratio of the ozone, the hydrogen peroxide and the iron-carbon filler is increased, the comprehensive treatment efficiency of the system is also remarkably improved; when the adding mass ratio of the ozone, the hydrogen peroxide and the iron-carbon filler reaches 4:2:3, the comprehensive treatment efficiency of the system reaches the optimum; when the addition mass ratio is more than 4:2:3, the treatment effect of the system is not obviously improved; therefore, the adding mass ratio of the ozone, the hydrogen peroxide and the iron-carbon filler is 4:2:3, which is a critical ratio.
Example 4
In this example, the amount of the printing and dyeing wastewater of a certain control enterprise in Hebei river is 30000m in total3And d, intake COD is 6000mg/L, and design effluent COD is 150 mg/L. The wastewater is formed by mixing dyeing wastewater, printing wastewater and rinsing wastewater, and has complex components. The wastewater contains pulp, dye, auxiliary agent, surfactant, residual bleaching agent, a small amount of acetic acid, sodium thiosulfide and other substances, is strong in basicity, high in chroma and poor in biodegradability, and is treated by adopting a regulating tank, pre-heterogeneous catalytic oxidation, integrated biochemical treatment of high-concentration wastewater and post-heterogeneous catalytic oxidation. The mass ratio of the ozone, the hydrogen peroxide and the iron-carbon filler is changed in a laboratory bench test, and the obtained experimental data are shown in the following table 6
TABLE 6 COD and NH of wastewater at different mass ratios of ozone, hydrogen peroxide and iron-carbon filler4Effect of removal of-N
Figure BDA0002561238510000092
Figure BDA0002561238510000101
As can be seen from Table 6 and FIG. 3, the COD removal rate and NH content of the system increased with the mass ratio of ozone, hydrogen peroxide and iron-carbon filler added4The N removal rate is also obviously improved; when the adding mass ratio of the ozone, the hydrogen peroxide and the iron-carbon filler reaches 4:2:3, the comprehensive treatment efficiency of the system reaches the optimum; and when the mass ratio of the additive is more than 4:2:3, the treatment effect of the system is not obviously improved.

Claims (5)

1. The comprehensive treatment system for the high-concentration wastewater difficult to degrade is characterized by comprising a pretreatment section, a front multi-phase catalytic oxidation integrated device, a high-concentration wastewater integrated biochemical treatment device and a rear multi-phase catalytic oxidation integrated device according to the wastewater treatment flow direction, wherein a gas distribution system and a catalytic filler are installed in a catalytic oxidation reaction tower of the front multi-phase catalytic oxidation integrated device, ozone gas enters from the bottom of a reaction tower through the gas distribution system, hydrogen peroxide is introduced as an oxidant when the ozone gas is introduced, the catalytic filler filled in the tower is an iron-carbon filler, the ozone adding amount is 0.1-10 mg/mg of COD wastewater, the hydrogen peroxide adding amount is 1-50 mg/mg of COD, and the adding mass ratio of the ozone, the hydrogen peroxide and the iron-carbon filler is 1:2: 2-4: 2: 3.
2. The integrated treatment system for high concentration wastewater difficult to degrade according to claim 1, wherein a submersible stirrer is installed in the adjusting hydrolysis contact tank of the integrated biochemical treatment device for high concentration wastewater.
3. The integrated treatment system for high-concentration wastewater difficult to degrade according to claim 1, wherein baffle plates are vertically arranged in the multiphase anaerobic baffled contact reaction tank of the integrated biochemical treatment device for high-concentration wastewater, and divide the tank body into a multi-compartment structure.
4. The integrated treatment system for high concentration wastewater difficult to degrade according to claim 1, wherein an aerobic filler and an aeration system are installed in the tank of the biological contact oxidation tank of the integrated biochemical treatment device for high concentration wastewater.
5. A method for comprehensively treating refractory high-concentration wastewater is characterized by comprising the following steps:
pre-treating;
the pretreated wastewater enters a pre-multiphase catalytic oxidation integrated device, macromolecule organic matters which are difficult to biodegrade are decomposed into micromolecule organic matters which are easy to be biodegraded by the synergistic action of ozone, hydrogen peroxide and iron carbon filler, the fallen carbon powder is discharged to a subsequent biochemical unit along with the oxidized wastewater, wherein, a gas distribution system and a catalytic filler are arranged in the catalytic oxidation reaction tower of the former multi-phase catalytic oxidation integrated equipment, ozone gas enters from the bottom of the reaction tower through the gas distribution system, when the ozone gas is introduced, hydrogen peroxide is introduced as an oxidant, the catalytic filler filled in the tower is iron-carbon filler, wherein the adding amount of ozone is 0.1-10 mg/mg COD wastewater, the adding amount of hydrogen peroxide is 1-50 mg/mg COD, and the adding mass ratio of ozone, hydrogen peroxide and iron carbon filler is 1:2: 2-4: 2: 3;
wastewater flowing to the high-concentration wastewater integrated biochemical treatment device sequentially passes through the adjusting hydrolysis tank, the multiphase anaerobic baffling contact reaction tank, the biological contact oxidation tank and the micro-aeration MBR tank, and forms a sludge membrane symbiotic microbial environment and a sludge system with multiple sludge ages in the biochemical system under the action of carbon powder and fillers to remove COD (chemical oxygen demand) and TN (total nitrogen) pollutants;
the biochemical effluent is discharged to a post-multiphase catalytic oxidation integrated device, in the device, macromolecular organic matters which are subjected to biochemical treatment and can not be degraded by renewable organisms are further oxidized into micromolecular organic matters, then the micromolecular organic matters flow back to a regulating hydrolysis tank to be removed under the action of microorganisms, and carbon powder falling off in the device flows back to a biochemical unit to become a biological carrier for use.
CN202010613151.XA 2020-06-30 2020-06-30 Comprehensive treatment method and system for refractory high-concentration wastewater Pending CN111762968A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010613151.XA CN111762968A (en) 2020-06-30 2020-06-30 Comprehensive treatment method and system for refractory high-concentration wastewater

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010613151.XA CN111762968A (en) 2020-06-30 2020-06-30 Comprehensive treatment method and system for refractory high-concentration wastewater

Publications (1)

Publication Number Publication Date
CN111762968A true CN111762968A (en) 2020-10-13

Family

ID=72723063

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010613151.XA Pending CN111762968A (en) 2020-06-30 2020-06-30 Comprehensive treatment method and system for refractory high-concentration wastewater

Country Status (1)

Country Link
CN (1) CN111762968A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102276051A (en) * 2011-06-13 2011-12-14 武汉纺织大学 Treatment method and treatment device for organic wastewater
US20120012525A1 (en) * 2009-05-22 2012-01-19 Zhiping Kuang Refuse landfill leachate wastewater treatment system and technology
CN107777830A (en) * 2016-08-29 2018-03-09 北京安宇通环境工程技术有限公司 A kind of high-concentration hardly-degradable pharmacy wastewater treatment method and system
CN108862774A (en) * 2018-07-13 2018-11-23 青岛万源环境科技有限公司 A kind of high-leveled and difficult sewage treatment equipment
CN214270590U (en) * 2020-06-30 2021-09-24 北京新林水务科技有限公司 Difficult degradation high concentration waste water integrated processing system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120012525A1 (en) * 2009-05-22 2012-01-19 Zhiping Kuang Refuse landfill leachate wastewater treatment system and technology
CN102276051A (en) * 2011-06-13 2011-12-14 武汉纺织大学 Treatment method and treatment device for organic wastewater
CN107777830A (en) * 2016-08-29 2018-03-09 北京安宇通环境工程技术有限公司 A kind of high-concentration hardly-degradable pharmacy wastewater treatment method and system
CN108862774A (en) * 2018-07-13 2018-11-23 青岛万源环境科技有限公司 A kind of high-leveled and difficult sewage treatment equipment
CN214270590U (en) * 2020-06-30 2021-09-24 北京新林水务科技有限公司 Difficult degradation high concentration waste water integrated processing system

Similar Documents

Publication Publication Date Title
KR101665636B1 (en) Wastewater pretreatment method and sewage treatment method using the pretreatment method
CN102126811B (en) Double-anoxic denitrification method and equipment for enhanced denitrification of sewage
CN109205954A (en) Light electrolysis catalysis oxidation, biochemical treatment high-concentration waste hydraulic art
WO2012155790A1 (en) Method for treating total nitrogen in wastewater in coal chemical industry by using microbes
CN112979065A (en) Garbage transfer station leachate full-treatment system
CN106277555A (en) The high efficiency, low cost processing method of a kind of coking chemical waste water and system
CN109179656A (en) A kind of high concentration organic nitrogen waste water dis posal technique
CN113772820B (en) Device and method for improving sludge concentration and inhibiting sludge expansion of biochemical system
CN214218490U (en) Landfill leachate treatment system
CN110642478A (en) Coupled treatment system and method for coking phenol-cyanogen wastewater by biochemical method and physicochemical method
CN111747600A (en) Ozone oxidation-biochemical coupling water treatment method
CN214270590U (en) Difficult degradation high concentration waste water integrated processing system
US20240059597A1 (en) Anaerobic ammonia oxidation treatment system for treating wastewater with high ammonia nitrogen and high cod
CN203295318U (en) Integrated denitrifying and dephosphorizing MBR device
CN110217939B (en) Improved AAO-based sewage nitrogen and phosphorus removal device and process
CN110282825B (en) Landfill leachate treatment method and system
CN111825216A (en) System and process for treating high-COD high-ammonia nitrogen wastewater
CN116143352A (en) Full-quantification combined treatment system and method for landfill leachate
CN116119888A (en) Combined treatment system and treatment method for post-concentration liquid of landfill leachate membrane
CN214880540U (en) Wastewater denitrification treatment system
CN212425594U (en) System for realizing anaerobic ammonia oxidation denitrification of low-ammonia-nitrogen wastewater by using side anaerobic high-pH and FA to inhibit NOB
CN111762968A (en) Comprehensive treatment method and system for refractory high-concentration wastewater
CN114085012A (en) Organic wastewater treatment system and organic wastewater treatment method
CN202576159U (en) Sludge-membrane co-exist deep denitrification device
CN112225405A (en) Micro-nano bubble-zero-valent iron coupling biological method effluent disposal system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination